Fibers and fabrics finished with a dicarboxylic reagent modified polyolefin wax



United States Patent 3 450,559 FIBERS AND FABRICS FINISHED WITH A DICAR-lvlvolgzYLlC REAGENT MODIFIED POLYOLEFIN A Gretchen S. Schaufelberger,Basking Ridge, NJ., assignor t; Iliniou Carbide Corporation, acorporation of New or No Drawing. Continuation-in-part of applicationSer. No. 330,248, Dec. 13, 1963. This application Nov. 2, 1965, Ser. No.506,119

Int. Cl. C03c 25/00; C0811 19/02, B44d 1/22 U.S. Cl. 117-126 4 ClaimsABSTRACT OF THE DISCLOSURE Textile fibers and fabrics finished with adicarboxylic acid modified polyolefin wax to impart characteristics suchas handle, appearance, drape, touch, softness, sheen, durability, shrinkresistance, and the like.

This application is a continuation-in-part of copending application Ser.No. 330,248, filed Dec. 13, 1963 which in turn is a continuation-in-partof application Ser. No. 203,440 filed June 19, 1962, both now abandoned,which in turn is a continuation-in-part of application Ser. No. 158,581filed Dec. 11, 1961, also now abandoned.

This invention relates to the finishing of fiber and articles made fromfibers such as textiles. More particularly, the invention relates tonovel finishing agents for fibers and textiles.

As disclosed in application Ser. No. 158,581 a wide variety ofsubstances can be coated with modified polyethylene wax. Substrates suchas those cellulosic and polymeric in nature were there disclosed to havebeen coated with this wax. The particular form of the substrate is ofcourse not critical. The present application relates to a specific formof substrate namely textile fiber. The basic nature of the fiber as acellulosic or polymeric substrate is not changed.

Fibers useful herein can be classified as natural, semisynthetic,synthetic or glass fibers and include natural organic fibers comprisingessentially cellulosic fibers (from vegetable sources) such as cotton,hemp, flax (linen), ramie, sisal, jute and the like; polymeric naturalorganic fibers e.g. proteinaceous fibers (from animal sources) such assilk (produced from the moth of the Bombyx species), wool and the like;polymeric semi-synthetic organic fibers comprising rayons or cellulosederivatives made from wood pulp or cotton linters such as regeneratedcellulose rayons such as viscose rayon and cuprammonium rayon, celluloseesters such as acetate rayon and cellulose ethers such as ethylcellulose; polymeric synthetic organic fibers e.g. nylons (polyamides),polyesters (reaction product of polybasic acids and glycols)polyethylene, polypropylene, vinyl chloride/vinyl acetate copolymer,vinyl chloride/acrylonitrile copolymer polyacrylonitrile, vinylchloride/vinylidene chloride copolymer, polyurethanes and the like; andglass fibers such as Fiberglas.

Finishing herein refers to treatment of fibers either per se or as atextile or fabric to impart new characteristics and properties such ashandle, appearance, drape, touch (surface lubricity, flexibility,compressibility and elastic recovery), softness, sheen, durability,shrink resistance, proofing against crushing, slip, water and moths.

Cationic salts of simple primary amines such as hexadecyl aminehydroacetate, salts of simple tertiary amines such as hexadecyldimethylamine hydroacetate, quaternary ammonium salts such as hexadecyldimethyl benzyl ammonium chloride, salts of amino acids such asmonostearoyl diethylene triamine dihydroacetaate, quarternary ammoniumsalts of amino amides such as ,B-diethylaminoethylstearamideethosulfate, salts of imidazolines such as ,u-heptadecyl, N-aminoethylimidazoline dihydroacetatae, quarternary derivatives of imidazolines,salts of amino esters such as B-dihydroxyethyl aminestearatehydroacetate and quaternary ammonium salts of amino esters haveheretofore been used as finishing agents. Practically all materials thatare in commercial use are derived from stearic acid. Hydrocarbon chainsof greater length have been sought but high cost and poor availabilityhave barred their general use despite promising experimental results.

It is an object, therefore, of the present invention to providefinishing agents of relatively very great molecular weight for improvingthe tear strength, edgewear resistance, needle burn resistance and flexabrasion resistance of fibers.

It is another object to provide textiles and fabrics having improvedhandle.

It is another object to increase the water repellancy of textiles andfabrics, especially of proteinaceous and cellulosic fiber textiles.

A fiber finishing agent has now been discovered comprising anunsaturated dicarboxylic reagent modified polyolefin wax. Textiles andfabrics having improved tear strength, edge-wear resistance, needle burnresistance and flex abrasion resistance are obtained by treating thetextile with an unsaturated dicarboxylic reagent modified polyolefinwax.

The term polyolefin is used in the present specification and claims todenote normally solid homopolymers of monoolefinically unsaturatedhydrocarbons as well as normally solid copolymers thereof, with one ormore other organic compounds copolymerizable therewith which containpolymer producing unsaturation, such as is present for example in carbonmonoxide and formaldehyde and in compounds containing the ethylenelinkage e.g. styrene, vinyl stearate, butene, vinyl acetate, vinylformate, methacrylatc, monobutyl maleate, 2-ethyl hexyl acrylate,N-methyl-N-vinyl acetamide, methacrylic acid, ethyl acrylate, acrylicacid, isoprene, butadiene, acrylamide, vinyl triethoxysilane,bicycloheptene, bicycloheptadiene, divinyl phosphonate and the like.Many other copolymerizable monomers which can be used in addition tothese illustrative compounds are well known in the art. Preferredpolyolefins in this invention contain at least 50 percent by weight of acombined alpha-mono-olefinically unsaturated hydrocarbon having from 2to 4 carbon atoms inclusive, i.e. butene-l, propylene and especiallyethylene. Where the wax to be modified is polyethylene the density ofthe polyolefin is critical and must be above 0.940.

The term modified polyolefin wax refers to low molecular weight waxese.g. molecular Weights from about 1000 to about 5000 of polyolefins asthat term is defined above which have been reacted with an unsaturateddicarboxylic reagent as defined below. The particular method ofpreparation of the unsaturated dicarboxylic reagent modified polyolefinWaxes used in the present invention is not critical. For example, thesewaxes can be prepared, in general, by reaction of an unsaturateddicarboxylic reagent with a low molecular weight polymer polymerizeddirectly to that weight, or a low molecular weight polymer formodification can be obtained by the pyrolysis or thermal degradation ofa high molecular weight polyolefin e.g. a polyethylene having a densityof 3 from 0.94 to 0.98 and higher. The pyrolysis is conveniently carriedout in a heated pyrolysis tube at about 450-600 C. but can be effectedin any known manner. The resulting waxes range in molecular weight fromabout 1000 to about 5000, and preferably from 1500 to 5000.

In a preferred method of preparing the preferred modified polyethylenewaxes, a polyethylene wax having a density above about 0.94 and amolecular weight of from about 1500 to 5000 is blended in the liquidphase, i.e., in the melt or in solution with from 1 to 25 percent byweight of an unsaturated dicarboxylic reagent e.g. maleic anhydride andreacted by being agitated therewith at temperatures of from about 130 C.to about 250 C. and preferably above 180 C. With lower densitypolyethylenes reaction temperatures of 80 C. and above are suitable.What is required is that the reaction mixture be agitatable. Theblending and agitation can be carried out in any manner which insuresintimate commingling of the reactants and good heat transfer throughoutthe reaction mass during the reaction time. For example, thepolyethylene wax can be dissolved in an inert liquid organic solvent forthe wax and carboxylic reagent such as toluene, xylene, cyclohexane,methylcyclohexane, isooctane and chlorinated hydrocarbon solvents suchas orthodichlorobenzene, 1,1,2-trichloroethane and a-chloronaphthalene.The dissolving of the polyethylene wax is most conveniently accomplishedat temperatures above 110 C. in aromatic solvents for higher densitypolyethylenes.

It is preferred to effect reaction in the melt in the absense of anorganic solvent by heating a high density polyethylene wax to itsmelting point (ca. 130 C.) and above, e.g. to 180 C. and stirring infrom 5 to percent, based on the wax, of an unsaturated dicarboxylicreagent e.g. maleic anhydride and continuing heating for 60-90 minutes.Temperatures of reaction either in solution or in the melt above about250 C. confer no added benefit in speed of reaction or quality ofmodified wax obtained and, hence, will not be ordinarily used. Themodification reaction can be effected under pressure to prevent unduevolatilization of the unsaturated dicarboxylic reagent or loss ofsolvent. The viscosity of the melted polyethylene waxes, e.g., 250-1000centipoises at 200 C. is such that rapid stirring of the unsaturateddicarboxylic reagent is easily accomplished. The exact manner or ofaddition of the reactants is not critical. Any excess unsaturateddicarboxylic reagent is removed after the reaction as by vacuumdistillation or like technique.

By the term unsaturated dicarboxylic reagent as used in the presentspecification and claims is meant an organic compound containing twocarboxyl groups (COOH) and having from 4 to 10 carbon atoms and at leastone double bond, e.g. maleic acid, tetrahydrophthalic acid, fumaricacid, glutaconic acid, itaconic acid, and the like and anhydrides of theunsaturated dicarboxylic acids e.g. maleic anhydride. All of theseunsaturated dicarboxylic reagents are capable of undergoing an additionreaction to one or more olefinic linkages occurring in polyethylenewaxes.

The application of the modified wax to fibers or textiles can be readilyaccomplished by use of a hot melt or solution of the wax and rollercoating, dip coating, spray coating or otherwise.

Alternatively and advantageously the limitations of hot melt or solutionapplication or incorporation can be avoided by use of an anionic,cationic or non-ionic emulsion of the modified wax as the coatingmixture. Typically water emulsions are prepared by melting together thecarboxylic reagent modified polyolefin wax and a fatty acid such as, forexample, formic, acetic, propionic, butyric, valeric, caproic,enanthylic, caprylic, pelargonic, capric, undecylic, lauric, trideoic,myristic, pentadecanoic, palmitic, megaric, stearic, nondecylic,arachidic, behenic, carnaubic, hyenic, carborceric, cerotic, laccroic,melissic, montanic, psyllic, acrylic crotonic, isocrotonic, vinylacetic,methylacrylic, tiglic, angelic, senecioic, hexenic, teracrylic,

4 hypogeic, oleic, elaidic, eurcic, brassidic, propiolic, propynoic,tetrolic, 2-butynoic, pentinoic, 2-pentiuoic, amylpropiolic, palmitotic,stearolic, behenolic, sorbic, linoleic and linolinic acids. These acideshave the general formula wherein n is an integer from 0 to 32 and x isan odd number from 5 to +1 with the proviso that when 11 :0, x=+1. Anamine soap is then added such as monoand triethanolamine,mono-isopropanolamine, diisopropanolamine, triisopropanol'amine,morpholine, N,N-dimethylethanolamine and N,N-diethylethanolamine. Themixture is stirred until thoroughly mixed or until it becomes clear.Other emulsifying aids such as polymeric glycols and ethoxylated soybeanoils can also be used depending on whether an anionic, cationic ornon-ionic emulsion system is desired. Water which has been heated toabout C. is added and the mass stirred under pressure. The mixture isthen vigorously agitated in a suitable device, e.g., a bladed mixercolloid mill or other shear producing apparatus to form the emulsion. Anunsaturated dicarboxylic reagent modified polyolefin wax solids contentof from 0.1 to 25 percent is preferred in emulsions to be used asfinishing agents.

The water emulsion of the modified wax is easily coated onto the fibersubstrate by any of the conventional techniques including brushing,dipping, spraying, roller coating and the like. The water of theemulsion is evaporated either by allowing the coated-on emulsion tostand at room temperature or preferably by force drying as by airmovement around and/or application of heat to the emulsion coating. Upondrying there remains a non-tacky and non-blocking coating which impartsimproved handle, lubricity and abrasion resistance to fibers.

Generally from about 0.01 to about 25% by weight of modified wax basedon the fabric weight is coated onto the fabric. Preferred amounts arebetween 0.1 and 10% by weight on the "same basis.

After application of the unsaturated dicarboxylic reagent modifiedpolyolefin wax to the fiber substrate it is preferred to subject thecoated substrate to a post-heating step, particularly by heating to atemperature above the melting point of the wax provided the fiber is notdegraded thereby. This enables a greater degree of flow of the wax intothe interstices of the fabric and facilitates reaction of the reactivegroups of the wax with the reactive groups of the fibers e.g. acid oranhydride groups on the wax with hydroxyl groups or acetate groups oncellulosic fibers such as cotton or rayon.

As mentioned above, the finishing of textile fibers improves the waterrepellency characteristics. Other aids can be simultaneously employedincluding N-octadecyl-N- ethylene urea, alkyl isocyanates, thiocyanates,organo-silicon compounds, aluminum oxides and soaps, copper soaps,chromium soaps, zirconium soaps and oxide, organo-halosilanes, rareearth metal soaps, petroleum and vegetable waxes, methylol stearamide,pyridium chlorides. Flameproofing agents can also be combined withmodified polyolefin wax prior to application to the textile fibers suchas boric acid/borax mixtures, ferric hydroxide, antimony oxychloride,stannic oxide hydrated, titanic hydroxide, bismuth trioxide hydrated,zinc stannate, aluminum bo rate, lead peroxide, cerium hydroxide,aluminum hydroxide, chromic hydroxide, silica hydrated, aluminumsilicate, magnesium silicate and magnesium ammonium phosphate and withthese pentachlorodiphenyl, neoprene, chlorinated paraffin, vinylchloride resins and aniline hydrochloride.

Other flameproofing agents include volatile phosphates and sulfamates.Mothproofing agents and mildewcides too can be applied with thefinishing agent such as inorganic fluorides,dichlorobenzene-sulfon-methylamide, p-aminobenzenesulfonamide,dichlorodiphenyl trichloroethane (DDT), pentachlorophenol and the sodiumsalt of pentachlorodihydroxy triphenylmethan-sulfonic acid. Alsorot-proofing agents such as copper salts of rosin and tall oil, terpinolhydrate as well as alkalies, formaldehyde, dyes, pigments, sequestrants,dispersants, starch, dextrin, glue, gums, china clay, Epsom salts,glycerol, soaps, soluble oils, antichlors, antifoaming and antistaticagents, batching oils, enzymes, lubricants, rust preventatives, spottingand weighting aids.

The present invention is illustrated by the following examples. Alylparts and percentages are by weight unless otherwise stated.

EXAMPLE 1 A maleic anhydride modified polyethylene wax was prepared byextruding a 0.96 density resin from a screw extruder through a hot tube48 inches in length, having a diameter of three inches and fitted withan axially positioned 2 and A5 inch diameter torpedo, at a rate of 32pounds per hour. The torpedo was heated to 425 C.

Sixty pounds of the resulting wax was reacted with 6 pounds of maleicanhydride for 90 minutes at 220 C. in a gallon autoclave equipped with aDowtherm jacket, and a 6 inch turbine agitator. The reaction product wasrecovered by stripping the excess maleic anhydride under 5 mm. Hgpressure and removing the reaction product. The modified wax contained2.7% carboxyl (calculated as succinic acid) and had a viscosity of 530centipoises at 140 C.

One hundred grams of the modified wax was mixed with grams ofmorpholine, 20 grams of oleic acid and 800 grams of water. The mixturewas charged to a pressure reaction vessel and heated to 150 C. withagitation and immediately cooled. There was obtained a white emulsionhaving a solids content of 14.7%.

The above emulsion was diluted to 10 percent by weight polyethylene wax.A piece of rayon triacetate fabric was immersed in the emulsion. Onesection of the fabric was air dried and then heated for one minute at350 F. A second section was only air dried. Both sections were wellcoated with an adherent covering of the modified wax. The heat-treatedfabric was smoother and had better handle. Puncture of the post-treatedfabric with a needle did not break the threads. Both sections of fabricwere waterproof.

EXAMPLE 2 Several solutions of the modified wax prepared in Example 1were prepared by diluting the emulsion to 2.5, 5 and 10% solids. Squaresof cotton fabric were immersed in each of these solutions. One-half ofeach square was air dried for two hours at room temperature. The otherhalf of each square was oven dried at 130 C. for 45 minutes. Thepost-treated fabric was water resistant, with applied water balling up."

While not necessary, post-heat treatment of coated fabric at 160l75 C.for 1 to 60 minutes provides a superior product in terms of tearstrength, edgewear resistance, needle burn resistance and flex abrasionresistance. Heat-treated fabrics retain these properties, includingwater-proofness, after laundering.

EXAMPLES 34 Example 2 was duplicated using a 0.3% solids emulsionprepared as above but using a cationic emulsifier, an ethoxylatedsoybean oil derivative mixed with acetic acid. Samples of cotton fabric(Example 3) and viscose rayon (Example 4) were immersed until the weightpickup of emulsion was 100%. Samples were dried at 175 F. for 3 minutes.Flex abrasion was measured according to ASTM D-1175-55T.

EXAMPLE 5 Strips of fiber glass cloth, (No. 181 weave, type 2967finish), 4" x 2", were immersed in emulsions of maleic anhydridemodified high density polyethylene wax as described in Example 1.Emulsion solids content and immersion conditions were adjusted such thatthe cloth picked up 0.5, 1.0, 2.5, 5.0 and 10.0 wt. percent solids.

The cloth samples were squeezed partly dry, then air dried at roomtemperature. The samples of dried cloth were then heat treated at C. for10 minutes in an air oven to fuse the polyethylene wax coating.

After treatment the samples were examined visually and by feel toqualitatively rate the softness. The fabric stiffness was quantitativelyrated also by the blending length test for fabrics (ASTM-1488-55T).

The fiber glass cloth sample treated with 0.5 wt. percent solids from acationic or anionic emulsion was significantly improved in softness,hand, or drape properties as shown in the following table:

Bending length, cm.

Percent solids Percent solids (ASTM (emulsion) (on fabric) Hand or "feel148855T) 0 Med. soft 4. 1

-0. 5 Soft 3. 2

l. 0 Med. soft 4. 2

2. 5 Increasing stiffness 5. 5

5. 0 From med. soft 6.0

The modified polyethylene wax coating functions as a lubricant andpermits slippage at fiber interfaces. The results show that the 0.5%emulsion solids level gave the softest fabric, and the fabric becamestiffer at higher levels.

Control I & II

Samples of cotton (I) and rayon (II) fabric without any finishing agentwere tested for flex abrasion resistance.

Control III & IV

Samples of cotton (III) and rayon (IV) fabric were immersed in anemulsion polymerized (high pressure) low density polyethylene. Resultswere as follows:

Flex abraision Resistance (cycles Example Solids on fabric to failure) 30. 3 1, 550 4 0. 3 2, 527 0 656 0. 3 864 0 395 0. 3 763 Other polyolefinwaxes such as polypropylene wax modified with unsaturated dicarboxylicreagents such as maleic acid provide similar results.

As indicated above not only are cellulosic fibers such as cotton andrayon improved in the present invention but proteinaceous substrate suchas wool are also improved. As an illustration, the application of a 2%by weight emulsion as prepared in Example 1 onto a woolen cloth impartsneedle burn resistance and improved handle.

Synthetic fibers can also be improved particularly in handle byapplication of the modified wax in accordance with the presentinvention. Thus, polypropylene, nylon, and polyester fabrics can beimproved in edgewear resistance, needle burn resistance and durabilityby the application of modified wax coatings.

What is claimed is:

1. Fabric comprising textile fibers thereon of from about 0.01 to about25 percent by weight, based on the weight of said fabric, of a finishingagent consisting essentially of a polyethylene wax having a density ofat least 0.940 and a molecular weight between 1000 and 5000 which hasbeen modified by reaction with from 1 to 25 percent by weight of anunsaturated dicarboxylic reagent having from 4 to 10 carbon atoms.

2. Fabric claimed in claim 1 wherein said fabric comprises organicfibers.

3. Fabric claimed in claim 1 wherein said fabric comprises glass fibers.

4. Fabric claimed in claim 1 wherein said polyolefin having a coatingwax is polyethylene wax and said reagent is maleic anhydride.

References Cited UNITED STATES PATENTS Huijser et a1 26082 Laner 117-126X Mattinson et a1. 117168 X Bohrer 117-139.5 X Jefferson et a1 117-139.5Wilder 106-270 X Johnson 117-139.5

8 Wolinsky 26028.5 Ross 117-139.5 Patterson et a1. 117138.8 Shippe eta1. 106270 WILLIAM D. MARTIN, Primary Examiner.

THEODORE G. DAVIS, Assistant Examiner.

US. Cl. X.R.

